Process for incorporation of uv-luminescent compounds in polymeric materials

ABSTRACT

The invention relates to a process for the preparation of luminescent textile fibres characterized in that the fibres are ated with a composition comprising (a) one or more luminescent lanthanide chelates containing three organic anionic ligands having at least one UV absorbing group and (b) one or more solvents.

The present invention relates to a process for the preparation of UVluminescent polymeric materials and their uses.

There is a need for furnishing textiles with covert effects, which mayact as security markings, as special effects or as decorations that onlybecome visible under UV irradiation.

It is therefore an object of the present invention to provide a dyeingcomposition comprising a substance which is invisible to the unaided eyebut yields a strong luminescence under UV exposure and which compositioncan be used for all conventional dyeing applications of polymericmaterials including textiles such as wool, silk, cellulosic materials,natural and synthetic fibres as well as for the mass dyeing of polymericmaterials including those used in textile and plastic applications.

The invention relates to a process for the preparation of luminescentpolymeric fibres characterised in that the fibres are treated with acomposition comprising

-   (a) one or more luminescent lanthanide chelates containing three or    four organic anionic ligands having at least one UV absorbing group    and-   (b) one or more solvents.

Preferably, component (a) is a compound of formula IL_(m)-Ln³⁺(Ch—)_(n)  (I).wherein Ln represents a lanthanide,

-   Ch⁻ is a negatively charged ligand containing at least one UV    absorbing double bond,-   n denotes 3 or 4, m denotes a number from 0 to 4,-   in case n is 3, m denotes a number from 0 to 4 and L is a neutral    monodentate or polydentate nitrogen-, oxygen- or sulfur-containing    ligand or, in case n is 4, m denotes 1 and L is a single-charged    cation.

More preferably, component (a) is a compound of formula II, III or IV

wherein Ln represents a lanthanide,

-   n denotes 3 or 4, m denotes a number from 0 to 4-   in case n is 3, m denotes a number from 0 to 4 and L is a neutral    monodentate or polydentate nitrogen-, oxygen- or sulfur-containing    ligand or, in case n is 4, m denotes 1 and L is a single-charged    cation,-   R₂, is hydrogen or C₁-C₆alkyl, and-   R₁ and R₃ are each independently of the other hydrogen, C₁-C₆alkyl,    CF₃, C₅-C₂₄aryl or C₄-C₂₄heteroaryl.

The compounds of formula I, II, III or IV can basically contain anyneutral monodentate or polydentate nitrogen-, oxygen- orsulfur-containing ligand such as, for example, unsubstituted orsubstituted pyridine, pyrazine, piperidine, quinoline, aniline,bipyridine, phenanthroline, terpyridine, imidazole, benzimidazole,bisimidazole, bisbenzimidazole, pyrimidine, bipyrimidine, naphthyridine,alkylamine, dialkylamine, trialkylamine, alkylene polyamine, dioxane,dimethylsulfoxide, dimethylformamide, phosphine-oxide derivative(trialkyl or triaryl), triazine, bistriazine, oxazole, bisoxazole,oxazoline, bisoxazoline and substituted derivatives thereof and allrelevant (poly)N-oxide derivatives of above cited ligands.

Particularly preferred are compounds of formula I, II, III or IV whereinn denotes 3 and L is a nitrogen-containing ligand.

Since L can be a polychelating ligand, like for example 4,4′-bipyridyl,the compounds of formula I, II, III and IV include multimetallicchelates, such as for example the compounds of formula XIII and XIV,containing two M^(III)-(diketone)₃ or M^(III)-(carboxylate)₃ unitsconnected via a bidentate ligand:

When n denotes 4, L as single-charged cation can be basically any metalcation (e.g. Li⁺, K⁺, Na⁺), unsubstituted or substituted ammonium (e.g.NH₄ ⁺, polyalkylammonium) or any protonated or alkylated monodentate orpolydentate ligand as described above.

Preferred positively charged ligands are piperidinium, ammonium,alkylammonium, dialkylammonium and, in particular, trialkylammonium.

Triethylammonium is especially preferred.

Particularly preferred are compounds of formula I, II, III or IV whereinL is a compound of formulae V to XII

-   -   or a caton of the formula H—N⁺(R₇)₃,        wherein R₄, R₅ and R₆ are each independently of the other        hydrogen, halogen, C₁-C₆alkyl, C₅-C₂₄aryl, C₆-C₂₄aralkyl,        C₁-C₆alkoxy, amino, dialkylamino or a cyclic amino group and R₇        is hydrogen, C₁-C₆alkyl, C₅-C₂₄aryl, C₆-C₂₄aralkyl or vinyl.

Alkyl groups as substituents R₁ to R₇ can be straight chain or branched.Examples which may be mentioned are methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, Isobutyl, tert-butyl, n-pentyl, neopentyl,isopentyl, n-hexyl and isohexyl.

Alkoxy groups as substituents R₄ to R₆ can be, for example, methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.

Examples of C₅-C₂₄aryl groups are phenyl, tolyl, mesityl, isityl,diphenyl, naphthyl and anthryl. Phenyl is preferred.

Heteroaryl group preferably contain 4 or 5 C atoms and one or twoheteroatoms selected from O, S and N. Examples are pyrrolyl, furanyl,thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl,pyridazinyl, indolyl, purinyl or chinolyl.

Aralkyl groups as substituents R₄ to R₇ can be, for example, benzyl,2-phenylethyl, tolylmethyl, mesitylmethyl and 4-chlorophenylmethyl.

Suitable dialkylamino groups are, for example, diethylamino,diisopropylamino, di-n-propylamino, N-methyl-N-ethylamino and, inparticular, dimethylamino or pyrrolidino.

Suitable cyclic amino groups are pyrrolidino and piperidino.

Halogen atoms as substituents R₄ to R₆ are preferably fluorine, chlorineor bromine, but in particular chlorine.

Preferred compositions according to the invention contain as component(a) a compound of formula II wherein L is a compound of formula V, VI,VII, VI II, IX, X, XI or XII wherein R₄, R₅ and R₆ are hydrogen, methyl,amino, pyrrolidino or dimethylamino or L is a cation of the formulaH—N⁺(R₇)₃ wherein R₇ is C₁-C₆alkyl.

Preferred components (a) are compounds of formula I, II, III or IVwherein Ln is Eu, Tb, Dy, Sm or Nd.

Furthermore, compounds of formula II and III are preferred, wherein R₁and R₃ are methyl, t-butyl, n-pentyl or phenyl.

R₂ in formula II is preferably hydrogen.

Particularly preferred as component (a) are the compounds of formulaXIII to CVI:

Some preferred derivatives of structures of type II and III, derivedfrom the above drawn preferred structures of type I, are compiled in thetable below: L DMAP DMAP DMAP DMAP DMAP Et₃NH⁺ Et₃NH⁺ Et₃NH⁺ Et₃NH⁺Et₃NH⁺ Ln Tb Eu Sm Dy Nd Tb Eu Sm Dy Nd Ch⁻

LIII XVIII LXII LXVIII LXXIII LXXIX LXXXIV LXXXIX LXXXXV CI

XV LVIII LXIII XVI LXXIV XXII LXXXV LXXXX LXXXXVI CII

LIV XVII LXIV LXIX LXXV LXXX XXI LXXXXI LXXXXVII CIII

LV LIX LXV LXX LXXVI LXXXI LXXXVI LXXXXII LXXXXVIII CIV

LVI LX LXVI LXXI LXXVII LXXXII LXXXVII LXXXXIII LXXXXIX CV

LVII LXI LXVII LXXII LXXVIII LXXXIII LXXXVIII LXXXXIV C CVIDMAP: 4-dimethylaminopyridine

Further suitable lanthanide chelates may contain

-   -   pyridine, aminopyridine, pyrrolidinopyridine, methylpyridine,        methoxypyridine, pyridine-N-oxide, bipyridine, phenanthroline,        imidazole or any other derived or similar N, O or S containing        mono- or polydentate ligand in place of DMAP        piperidinium, ammonium, alkylammonium, dialkylammonium,        trialkylammonium, pyridinium or any other similar N containing        protonated species in place of Et₃NH⁺

For certain applications it is recommendable to use a combination ofdifferent lanthanides, for example Eu and Tb. Such a mixture increasesthe degree of security of the hidden colourations, the sophistication ofthe security level and multiplies the coding possibilities.

The compounds of formula I, II, III and IV are known, for instance fromWO 96/20942 and from C. R. Hurt et al., Nature 212, 179-180 (1966), orcan be prepared by methods known per se. For example, a ligand such asacetylacetone, benzoylacetone, dibenzoylmethane, dipivaloylmethane,salicylic acid, valeric acid or caproic acid can be reacted undersuitable conditions with a rare earth metal halide such as a lanthanidetrichloride to produce the rare earth metal chelate. Further reactionwith the monodentate or polydentate nitrogen-, oxygen- orsulfur-containing ligand L thus yielding the rare earth metal chelatecompounds of formula I, II, III and IV.

The luminescent lanthanide chelate can be applied as a powder, as asolution or as a dispersion.

Accordingly, component (b) may be water, an organic solvent, a mixtureof two or more organic solvents or a mixture of water and one or moreorganic solvents.

Preferably, component (b) is water, one or more water-miscible organicsolvents or a mixture of water and one or more water-miscible organicsolvents.

Suitable organic solvents include alcohols, glycols, ether alcohols,sulfoxides, amides, amines, heterocyclic solvents, ketones, ethers,esters, nitriles and aliphatic, cycloaliphatic and aromatichydrocarbons.

Examples of suitable organic solvents are methanol, ethanol, n-propanol,isopropanol, n-butanol, glycerol, ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, polyethylene glycol,polypropylene glycol, ethylene glycol monoethylether, polyethyleneglycoldimethyether, ethoxybutanol, 2-butoxyethanol, dimethylsulfoxide (DMSO),dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone(NMP), acetone, 2-butanone, diethylether, di-n-propylether,tetrahydrofurane (THF), ethyl acetate, ethyl propionate, acetonitrile,pyridine, n-pentane, n-hexane, cyclohexane, benzene and toluene.

The water-miscible organic solvent is preferably an aliphatic alcohol,etheralcohol, glycol, aliphatic ketone, carboxylic acid ester,carboxylic acid amide, aliphatic nitrile, aliphatic polyether oraliphatic sulfoxide.

Particularly preferred water-miscible organic solvents are ethanol,2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone,ethyl acetate, tetrahydrofurane (THF), dimethylformamide (DMF),dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile,polyethyleneglycol dimethyether and dimethylsulfoxide (DMSO).

The compositions according to the invention may, in addition tocomponents (a) and (b), comprise one ore more colorants (c).

Suitable colorants are the well-known pigments and dyes includingmixtures of different pigments and dyes.

In the compositions according to the present invention the amounts ofcomponents (a) and (b) and where appropriate (c) and/or furtheringredients (d) can vary within wide ranges.

For a mass-dyeing process, the compositions according to the presentinvention consist of component (a). Optionally, further ingredients (c)and/or (d) may also be added together with (a) in order to givesimultaneous supplementary propertie(s) to the polymeric material inaddition to the UV-luminescence.

For a dyeing process, preferred compositions contain 0.01 to 20.0%, morepreferably 0.05 to 10% and in particular 0.1 to 5.0%, by weight ofcomponent (a) and 80.0 to 99.99%, more preferably 90.0 to 99.95% and inparticular 95.0 to 99.9%, by weight of component (b), based on the totalamount of components (a)+(b).

The amount of component (c) depends on the type of substrate as well ason the specific pigment or dye. Advantageous amounts will generally be0.01% to 15% by weight and especially 0.1% to 10% by weight, of colorantbased on the weight of fibre.

Further ingredients (d) which may be present in the compositionsaccording to the invention are e.g. optical brighteners, biocides,bactericides, fungicides insecticides and fragrance.

The compositions containing at least one lanthanide chelate can beprepared by any suitable method known to those of ordinary skill in theart. For example, the components of the composition can be combined andmixed in a suitable mixer or blender.

The compositions according to the invention are useful for impregnatingmanufactured natural, artificial and especially synthetic hydrophobicmaterials, especially textile materials.

Textile materials composed of blend fabrics comprising such manufacturednatural polymer or synthetic hydrophobic fiber materials can likewise beimpregnated with the formulations of the invention.

Useful manufactured natural polymer textile materials are especiallywool, cotton, silk, cellulose acetate and cellulose triacetate.

Synthetic hydrophobic textile materials are especially linear aromaticpolyesters, for example polyesters formed from a terephthalic acid andglycols, particularly ethylene glycol, or condensation products ofterephthalic acid and 1,4bis(hydroxymethyl)cyclohexane; polycarbonates,for example those formed from α,α-dimethyl-4,4′-dihydroxydiphenylmethaneand phosgene; or fibres based on polyvinyl chloride or polyamide.

The formulations according to the invention are applied to the textilematerials according to known dyeing processes. For example, polyesterfibres are exhaust dyed from an aqueous dispersion in the presence ofcustomary anionic or nonionic dispersants with or without customarycarriers at temperatures between 80 and 140° C., preferably between 120and 135° C. Cellulose acetate is preferably dyed at between 60 to 85° C.and cellulose triacetate at up to 115° C.

The formulations used according to the invention are useful for dyeingby the thermosol, exhaust and continuous processes and for printingprocesses. The exhaust process is preferred. The liquor ratio depends onthe apparatus, the substrate and the make-up form. However, the liquorratio can be chosen to be within a wide range, for example in the rangefrom 4:1 to 100:1, but it preferably is between 6:1 to 25:1.

The textile material mentioned may be present in the various processingforms, for example as a fibre, yam or web or as a woven orloop-formingly knitted fabric.

The luminescent lanthanide chelates of the invention are likewise usefulfor mass-dyeing of plastics.

Accordingly, the invention further relates to a process for thepreparation of luminescent plastics characterized in that the plasticsmaterial is extruded in the presence of 0.01-10.0 % by weight, based onthe amount of plastics material, of a compound of formula I, II, III orIV.

Plastics useful for mass dyeing include for example dyeable highmolecular weight organic materials (polymers) having a dielectricconstant ≧2.5, especially polyester, polycarbonate (PC), polystyrene(PS), polypropylene (PP), polymethyl methacrylate (PMMA), polyamide,polyethylene, polypropylene, styrene/acrylonitrile (SAN) oracrylonitrile/butadiene/styrene (ABS). Preference is given to polyesterand polyamide. Particular preference is given to linear aromaticpolyesters obtainable by polycondensation of terephthalic acid andglycols, especially ethylene glycol, or condensation products ofterephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane, for examplepolyethylene terephthalate (PET) or polybutylene terephthalate (PBTP);polycarbonates, for example polycarbonates formed fromα,α-dimethyl-4,4′-dihydroxydiphenylmethane and phosgene; polymers basedon polyvinyl chloride or polyamide, for example nylon 6 or nylon 6.6,polystyrene (PS) or polypropylene (PP).

Very particular preference is given to plastics based on linear aromaticpolyesters, for example those formed from terephthalic acid and glycols,particularly ethylene glycol, or condensation products of terephthalicacid and 1,4-bis(hydroxymethyl)cyclohexane, polymethyl methacrylate(PMMA), polypropylene (PP) or polystyrene (PS).

The plastics are dyed for example by mixing the luminescent lanthanidechelate according to component (a) into these substrates using rollmills or mixing or grinding apparatus whereby the lanthanide chelatesare dissolved or finely dispersed in the plastic. The plastic with theadmixed dyes is then processed in a conventional manner, for example bycalendering, pressing, extrusion, spread coating, spinning, casting orinjection moulding, whereby the dyed material acquires its ultimateshape. The mixing of the components can also be effected directly priorto the actual processing step, for example by continuously meteringsolid, for example pulverulent, lanthanide chelates and a granulated orpulverulent plastic and also optionally additional substances such asfor example additives simultaneously directly into the inlet zone of anextruder where the mixing-in takes place just prior to the processing.In general, however, prior mixing of the lanthanide chelates into theplastic is preferable, since more uniformly impregnated substrates areobtainable.

The invention further relates to luminescent textile fibre and toluminescent plastic prepared by the process described above.

The present invention makes it possible to incorporate colourless orcoloured hidden marks into various colourless, white, pale coloured ordark coloured substrates, which can be revealed under UV exposure.

The claimed process is particularly useful for the manufacture ofsecurity fibres or security threads that can be applied to fiduciarydocuments or other materials.

Security fibres are incorporated in fiduciary documents or othermaterials for the purpose of ensuring identification, an authentication,a protection against forgery, imitation or falsification. Securitythreads are continuous threads or strips of film introduced intofiduciary documents for the same purpose as security fibres.

The expression “fiduciary documents” denotes papers, such as papers forbank notes, cheques, shares, bills, stamps, official documents, identitycards, passports, record books, notes, tickets, vouchers, bulletins,accounting books as well as credit, payment, access or multifunctionalcards, and similar documents which necessarily involve a high degree ofsecurity.

The manufacture of security fibres or security threads can beaccomplished by known methods as described, for example, in U.S. Pat.Nos. 4,655,788, 5,759,349 and 6,045,656, EP-A 185 396 and EP-A 1 013824.

Incorporation of the lanthanide chelate compound can be carried out byconventional dyeing or printing processes.

Suitable fibres for the claimed process can be obtained from wood orvegetable pulp, cellulose pulp, cotton, linen or synthetic fibres.

Preferably, paper fibres or synthetic fibres are used.

In a particularly preferred embodiment the process according to claim 1is used for the preparation of anti-counterfeit documents, cards,cheques or banknotes.

The compositions according to the invention distinguish from analogousprior art compositions by outstanding luminescence quantum yield,long-lasting luminescence and high luminescence intensity.

The following Examples illustrate the invention.

Ink Composition A:

Concentrate of compound XVII in 1,2-propylene glycol

1 g of compound VIII is dissolved in 99 g of 1,2-propyleneglycol underheating at 100° C. for 1 hour. The clear yellow solution is allowed tocool down and after filtration (clarification) provides the stable InkComposition A which exhibits an intense red luminescence under UV light.This concentrate can be further used in either solvent based or aqueousbased conventional or high-tech (ink-jet) printing formulations forpaper, textile, leather, wood, plastic or other compatible substrates.

EXAMPLE 1

The impregnation of a cellulosic bobbin (0.75 kg cotton thread 40tex) isperformed at 35° C. for 20 min in an alternated circulation dyeingapparatus (Callebault de Blicquy) (3 min cycle) with a liquour ratio of1 to 10. The liquour contains 4.5% of the compound of formula XVII

in 2-butoxy-ethanol.

After treatment, centrifugation and air-drying of the bobbin, strongred-orange fluorescence is observed under UV light.

EXAMPLE 2

The impregnation of a silk thread (10 g) is performed at 25° C. for10-60 min in the same liquour and liquour ratio to textile material asdescribed in Example 1. After treatment, centrifugation and air-dryingof the thread reveals strong red-orange fluorescence under UV light.

EXAMPLE 3

The impregnation of a patchwork fabric containing several distinct bandsof synthetic, artificial, natural (vegetal and animal) fibers (20 g) isperformed at 25° C. for 10-60 min in the same liquour and liquour ratioto textile material as described in Example 1. After treatment,centrifugation and air-drying of the patchwork reveals on most fibersstrong red-orange fluorescence under UV light.

Equivalent results are obtained from similar processes using otherlanthanide complexes, exhibiting other emission wavelength underirradiation in the UV (e.g. terbium, dysprosium, samarium, neodymium).

EXAMPLE 4

High Temperature Dyeing (HTD) of a Polyester (PES) Filament (135° C., 60min)

A PES filament (10 g) is introduced in a 250 mL bottle tight againstleakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex of formula XVII dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogencarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated PES filament exhibits a strong red-orangefluorescence under irradiation at 365 nm.

EXAMPLE 5

High Temperature Dyeing (HTD) of a Velvet PES Fabric (135° C., 60 min)

A velvet PES fabric (10 g) is introduced in a 250 ml bottle tightagainst leakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 mL) containing 3-5% of the        lanthanide complex of formula XVII dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated PES filament exhibits a strong red-orangefluorescence under irradiation at 365 nm.

EXAMPLE 6

High Temperature Dyeing (HTD) of a Velvet PES Fabric (135° C., 60 min)

A white velvet PES fabric (10 g) is introduced in a 250 mL bottle tightagainst leakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex XV    -    dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogencarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated velvet PES fabric is white and exhibits a stronggreen fluorescence under irradiation at 254 nm.

EXAMPLE 7

High Temperature Dyeing (HTD) of a Polyamide (PA) Tricot (135° C., 60min)

A PA tricot (10 g) is introduced in a 250 mL bottle tight againstleakage, containing 200 mL of dyeing bath (i.e. bath ratio 1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 mL) containing 3-5% of the        lanthanide complex XVII dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogencarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated PA tricot exhibits a strong red-orangefluorescence under irradiation at 365 nm.

EXAMPLE 8

High Temperature Dyeing (HTD) of a PA Tricot (135° C., 60 min)

A white PA tricot (10 g) is introduced in a 250 ml bottle tight againstleakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 mL) containing 3-5% of the        lanthanide complex XV dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l A of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l A sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated PA tricot is white and exhibits a greenfluorescence under irradiation at 254 nm.

EXAMPLE 9

High Temperature Dyeing (HTD) of a Transparent Colourless PA Thread(135° C., 60 min)

A transparent colourless PA thread (10 g) is introduced in a 250 mlbottle tight against leakage, containing 200 ml of dyeing bath (i.e.bath ratio 1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex XVII dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated transparent PES thread exhibits a strongred-orange fluorescence under irradiation at 365 nm.

EXAMPLE 10

Incorporation of XVII in Polyamide (PA) by Mass-Dyeing Process

Extruded Ultramid B3K in the presence of 2% of the lanthanide complexXII for 2 min at 260° C. results in red-orange fluorescence uponirradiation at 365 nm.

EXAMPLE 11

Incorporation of XVII in Polystyrene (PS) by Mass-Dyeing Process

Extruded Polystyrol H165 in the presence of 2% of the lanthanide complexXVII for 5 min at 300° C. results in red-orange fluorescence uponirradiation at 365 nm.

EXAMPLE 12

Incorporation of XVII in Polypropylene (PP) by Mass-Dyeing Process

A homogenised mixture of polypropylene granules (200 g) and compoundXVII (2 g) is introduced in the fusion chamber (200° C.) of a 3 mm cableextruder. After cooling in a water bath, the thus obtained rigid cableis cut into granules again, which are in turn introduced in the fusionchamber (230° C.) of a filament extruder. The thus obtained transparentmultifilament thin polypropylene thread (8 dtex) exhibits a strongred-orange fluorescence upon excitation at 365 nm.

EXAMPLE 13

Incorporation of XVII in Polypropylene (PP) by Mass-Dyeing Process

Similar process and resulting fluorescent properties are obtained withsimultaneous use of Titanium dioxide together with compound XVII.

EXAMPLE 14

Incorporation of XVII in Poly(Methylmethacrylate) (PMMA) by Mass-DyeingProcess

Extruded Plexiglas 6N in the presence of 2% of the lanthanide complexXVII for 5 min at 260° C. results in red-orange fluorescence uponirradiation at 365 nm.

EXAMPLE 15

Incorporation of XVII in Acrylonitrile/Butadiene/Styrene-Copolymer (ABS)by Mass-Dyeing Process

Extruded Terluran 877M in the presence of 2% of the lanthanide complexXVII for 5 min at 220° C. results in red-orange fluorescence uponirradiation at 365 nm.

EXAMPLE 16

High Temperature Dyeing (HTD) of a Coloured PES Thin Thread (135° C., 60min)

A thin cyan PES thread (10 g)—previously mass-dyed with a mixture ofIrgalite Blue GLGP (C.I. Pigment Blue 15:3), titanium dioxide (C.L.Pigment White 6) and carbon black (C.I. Pigment Black 7)—is introducedin a 250 ml bottle fight against leakage, containing 200 ml of dyeingbath (i.e. bath ratio 1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex XV dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/Il of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/Il sodium hydrogencarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated thin cyan PES thread is cyan and exhibits a stronggreen fluorescence under irradiation at 254 nm and no fluorescence underirradiation at 365 nm.

EXAMPLE 17

High Temperature Dyeing (HTD) of a Coloured PES Thin Thread (135° C., 60min)

A thin black PES thread (10 g)—previously mass-dyed with a pigmentmixture containing titanium dioxide (C.I. Pigment White 6) and carbonblack (C.I. Pigment Black 7)—is introduced in a 250 ml bottle tightagainst leakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex XV dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated thin black PES thread is black and exhibits astrong green fluorescence under irradiation at 254 nm and nofluorescence under irradiation at 365 nm.

EXAMPLE 18

High Temperature Dyeing (HTD) of a Coloured PES Thin Thread (135° C., 60min)

A thin yellow PES thread (10 g)—previously mass-dyed with FilesterYellow RNB(C.I. Pigment Yellow 147)—is introduced in a 250 ml bottletight against leakage, containing 200 ml of dyeing bath (i.e. bath ratio1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex XV dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogencarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated thin yellow PES thread is yellow and exhibits astrong green-yellow fluorescence under irradiation at 254 nm and nofluorescence under irradiation at 365 nm.

EXAMPLE 19

High Temperature Dyeing (HTD) of a PES Filament (135° C., 60 min)

A PES filament (10 g) is introduced in a 250 ml bottle tight againstleakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to 20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex    -    dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 mL) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated PES filament exhibits a strong red-orangefluorescence under irradiation at 365 nm.

EXAMPLE 20

High Temperature Dyeing (HTD) of a PES Filament (135° C., 60 min)

A white PES filament (10 g) is introduced in a 250 ml bottle tightagainst leakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a NMP suspension (5 to 30 ml) containing 2% of the lanthanide        complex    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated white PES filament is white and exhibits apink-red fluorescence under irradiation at 254 nm and no fluorescenceunder irradiation at 365 nm.

EXAMPLE 21

High Temperature Dyeing (HTD) of a PES Filament (135° C., 60 min)

A white PES filament (10 g) is introduced in a 250 ml bottle tightagainst leakage, containing 200 ml of dyeing bath (i.e. bath ratio 1 to20).

The dyeing bath is prepared as a mixture of the following two solutions:

-   -   a solvent-based solution (5 to 30 ml) containing 3-5% of the        lanthanide complex    -    dissolved in NMP    -   an aqueous solution at pH=4.5 (195 to 170 ml) containing        -   0.6 g/l of Univadin DP (Ciba Specialty Chemicals)        -   2.5 g/l of Cibatex AB 45 (Ciba Specialty Chemicals)        -   0.4 g/l sodium hydrogenocarbonate

The bottle is installed in a rotating high temperature dyeing autoclavewith a starting bath temperature of 70° C. The temperature is thenraised to 135° C. over 30 min and kept stable for further 1 hour. Thetreatment temperature is finally decreased down to 40° C. over 15 min,after which the thread is removed from the bottle, rinsed for 5 min withwarm water (35° C.), spin dried and finally dried with hot air (90-105°C.). The thus treated white PES filament is white and exhibits a greenfluorescence under irradiation at 254 nm and no fluorescence underirradiation at 365 nm.

EXAMPLE 22

High Temperature Dyeing (HTD) of PES (135° C., 60 min)

All above experiments of High Temperature Dyeing are also realisedwithout using NMP, by a similar preparation method to that of DisperseDyes, and by replacing the Disperse Dye with the UV fluorescentlanthanide chelate to be applied.

EXAMPLE 23

Transfer printing with UV fluorescent lanthanide chelates is performedby using transfer printing formulations containing one or more UVfluorescent lanthanide chelates. These formulations are prepared in asimilar way to conventional transfer printing formulations, either byusing one or more lanthanide chelates in place of disperse dyes, or byusing one or more lanthanide chelates in addition to the dispersedye(s).

EXAMPLE 24

Preparation of a Multi-Component Security Thread

A polymer mixture (e.g. copolymerised polyamide Akulon®, supplied byAkzoplastiks) is distributed to three extruders and the granules aremelted. The melts indicated for the outer components of the thread areeach mixed with 3% by weight of a compound of formula (XVII) in such away that it dissolves homogeneously in the polyamide melt. Afterextrusion of the multi-component threads a security thread is obtainedthe edge strips of which fluoresce under UV light whereas the centralstrip does not show any fluorescence. Co-extrusion of the lanthanidechelate(s) with one or more dyes or pigments provides coloured threadswhich are similarly fluorescent under UV light.

EXAMPLE 25

Preparation of a Multi-Component Security Thread

As described in Example 24, a security thread is prepared by extrusionof a polyamide melt containing 3% by weight of a 1:1 mixture of acompound of formula (XVII) and a compound of formula (XV). Uponirradiation of UV light of different wavelengths red and/or greenfluorescence is observed.

1. A process for the preparation of luminescent polymeric fibres,wherein the fibres are treated with a composition comprising (a) one ormore luminescent lanthanide chelates containing three or four organicanionic ligands having at least one UV absorbing group and (b) one ormore solvents.
 2. A process according to claim 1, wherein component (a)is a compound of formula IL_(m)-Ln³⁺(Ch⁻)_(n)  (I), wherein Ln represents a lanthanide, Ch⁻ is anegatively charged ligand containing at least one UV absorbing doublebond, n denotes 3 or 4, m denotes a number from 0 to 4, wherein when nis 3, m denotes a number from 0 to 4 and L is a neutral monodentate orpolydentate nitrogen-, oxygen- or sulfur-containing ligand or, when n is4, m denotes 1 and L is a single-charged cation.
 3. A process accordingto claim 1, wherein component (a) is a compound of formula I, II, III orIV

wherein Ln represents a lanthanide, n denotes 3 or 4, m denotes a numberfrom 0 to 4, in which when n is 3, m denotes a number from 0 to 4 and Lis a neutral monodentate or polydentate nitrogen-, oxygen- orsulfur-containing ligand or, when n is 4, m denotes 1 and L is asingle-charged cation, Ch⁻ is a negatively charged ligand containing atleast one UV absorbing double bond, R₂, is hydrogen or C₁-C₆alkyl, andR₁ and R₃ are each independently of the other hydrogen, C₁-C₆alkyl, CF₃,C₅-C₂₄aryl or C₄-C₂₄heteroaryl.
 4. A process according to claim 3,wherein component (a) is a compound of formula I, II, III or IV whereinn denotes 3 and L is a nitrogen-containing ligand.
 5. A processaccording to claim 3, wherein component (a) is a compound of formula I,II, III or IV wherein L is a compound of formulae V to XII

 or a cation of the formula H—N⁺(R₇)₃, wherein R₄, R₅ and R₆ are eachindependently of the other hydrogen, halogen, C₁-C₆alkyl, C₅-C₂₄aryl,C₆-C₂₄aralkyl, C₁-C₆alkoxy, amino, dialkylamino or a cyclic amino groupand R₇ is hydrogen, C₁-C₆alkyl, C₅-C₂₄aryl, C₆-C₂₄aralkyl or vinyl.
 6. Aprocess according to claim 5, wherein component (a) is a compound offormula II wherein L is a compound of formula V, VI, VII, VIII, IX, X,XI or XII wherein R₄, R₅ and R₆ are hydrogen, methyl, amino, pyrrolidinoor dimethylamino or L is a cation of the formula H—N⁺(R₇)₃ wherein R₇ isC₁-C₆alkyl.
 7. A process according to claim 3, wherein component (a) isa compound of formula I, II, III or IV wherein Ln is Eu, Tb, Dy, Sm orNd.
 8. A process according to claim 3, wherein component (a) is acompound of formula II or III wherein R₁ and R₃ are methyl, t-butyl,n-pentyl or phenyl.
 9. A process according to claim 3, wherein component(a) is a compound of formula II wherein R₂ is hydrogen.
 10. A processaccording to claim 3, component (a) is a compound of formula XIII to LII


11. A process according to claim 1, wherein component (b) is water, oneor more water-miscible organic solvents or a mixture of water and one ormore water-miscible organic solvents.
 12. A process according to claim11, wherein the water-miscible organic solvent is an aliphatic alcohol,etheralcohol, glycol, aliphatic ketone, carboxylic acid ester,carboxylic acid amide, aliphatic nitrile, aliphatic polyether oraliphatic sulfoxide.
 13. A process according to claim 11, wherein thewater-miscible organic solvent is selected from the group consisting ofethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone,2-butanone, ethyl acetate, tetrahydrofurane (THF), dimethylformamide(DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile,polyethyleneglycol dimethylether and dimethylsulfoxide (DMSO).
 14. Aprocess according to claim 1, wherein the composition contains 0.01 to20.0% by weight of component (a) and 80.0 to 99.99% by weight ofcomponent (b), based on the total amount of components (a)+(b).
 15. Aprocess according to claim 1, wherein the composition containsadditionally (c) one or more colorants.
 16. A process for thepreparation of luminescent plastics, wherein the plastics material isextruded in the presence of 0.01-10.0% by weight, based on the amount ofpolymeric material, of a compound of formula II or III according toclaim
 3. 17. A luminescent textile fibre prepared by the processaccording to claim
 1. 18. A luminescent plastic prepared by the processaccording to claim
 16. 19. A process according to claim 1 wherein thepolymeric fibres are paper fibres or synthetic fibres.
 20. A method forthe preparation of anti-counterfeit documents, cards, cheques orbanknotes which comprises incorporating therein a luminescent polymericfibre prepared by the process according to claim 1.